Hydrothermal syntheses of the magadiite, a layered silicate structure, were conducted in the presence of a heteroatom source (SnCl4.5H2O) with the intention of investigating its influence on the resulting material, as well as the possibility of isomorphous replacement of Si by Sn atoms in the abovementioned structure. For comparison, unmodified magadiite, Al-containing magadiite, and impregnated magadiite were synthesized. The magadiite structure was identified for samples with Sn/Si ratios up to 0.015. Synthetic methods applied to Sn-modified materials were found to be unsuitable for the introduction of Al. The characterization methods used were X-ray diffraction, temperature-programmed reduction, and 29Si magic angle spinning nuclear magnetic resonance and these revealed the substitution of Si by Sn in the silica layers. No additional acid centers on the surfaces of the modified samples were detected, suggesting the presence of the desired four-coordinate Sn in the silica layers.

Deciphering the localisation of solid and dissolved impurities on the micron-scale in glacial ice remains a challenge, but is critical to understand the integrity of ice core records and internal deformation. Here we report on the state-of-the-art in microstructural impurity research by highlighting recent progress in bringing together cryo-Raman spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We show the potential of both methods and discuss possibilities to improve inter-method approaches aiming for a more holistic understanding of the evolution of impurity localisation throughout the ice column, including post-depositional processes. In this framework, we elaborate on future research priorities such as LA-ICP-MS imaging on firn samples and integrating a large cryo-cell with imaging capabilities.

During the past 20 years, multi-channel radar emerged as a key tool for deciphering an ice sheet's internal architecture. To assign ages to radar reflections and connect them over large areas in the ice sheet, the layer genesis has to be understood on a microphysical scale. Synthetic radar trace modelling based on the dielectric profile of ice cores allows for the assignation of observed physical properties’ variations on the decimetre scale to radar reflectors extending from the coring site to a regional or even whole-ice-sheet scale. In this paper we rely on the available dielectric profiling data of the northern Greenland deep ice cores: NGRIP, NEEM and EGRIP. The three records are well suited for assigning an age model to the stratigraphic radar-mapped layers, and linking up the reflector properties to observations in the cores. Our modelling results show that the internal reflections are mainly due to conductivity changes. Furthermore, we deduce fabric characteristics at the EGRIP drill site from two-way-travel-time differences of along and across-flow polarized radarwave reflections of selected horizons (below 980 m). These indicate in deeper parts of the ice column an across-flow concentrated c-axis fabric.

The validity of any glaciological paleo proxy used to interpret climate records is based on the level of understanding of their transfer from the atmosphere into the ice sheet and their recording in the snowpack. Large spatial noise in snow properties is observed, as the wind constantly redistributes the deposited snow at the surface routed by the local topography. To increase the signal-to-noise ratio and getting a representative estimate of snow properties with respect to the high spatial variability, a large number of snow profiles is needed. However, the classical way of obtaining profiles via snow-pits is time and energy-consuming, and thus unfavourable for large surface sampling programs. In response, we present a dual-tube technique to sample the upper metre of the snowpack at a variable depth resolution with high efficiency. The developed device is robust and avoids contact with the samples by exhibiting two tubes attached alongside each other in order to (1) contain the snow core sample and (2) to access the bottom of the sample, respectively. We demonstrate the performance of the technique through two case studies in East Antarctica where we analysed the variability of water isotopes at a 100 m and 5 km spatial scales.

The European Project for Ice Coring in Antarctica (EPICA) focuses on the drilling of two deep ice cores, the first at Dome C and the second at Kohnen station (75°00’ S, 0°04’ E) in Dronning Maud Land (DML). This paper deals with stable-isotope records from ice cores drilled in DML. In the first season, the deep EPICA DML core reached a depth of 450 m, recovering ice approximately 7000 years old. Generally, the δ18O record indicates a stable Holocene climate and shows low variability. However, during the last 4000 years (based on a preliminary time-scale) the δ18O values decrease continuously by about 0.6%, and the deuterium excess values increase by about 0.5%. The correlation between δ18O and the deuterium excess d is investigated for a 50m long core section and the near-surface snow. High-pass filtered profiles are positively correlated, whereas the correlation between low-pass filtered profiles is negative. A post-depositional effect due to diffusion processes can be seen in a sub-annually resolved profile from snow-pit samples. Changes in the seasonality of the evolution of the snow cover and the consequences for stable-isotope content are demonstrated with data from ice core B31.

The paper focuses on studies of snow-pit samples and shallow firn cores taken during the 1995-96 and 1996-97 field seasons at Amundsenisen, Dronning Maud Land, Antarctica. The dating of the firn is based on the artificial tritium distribution in the snow cover and on several reference horizons identified by electrical measurements. The early 1964 through 1965 horizon is marked by the deposition of sulfate released to the atmosphere during the eruption of the Agung volcano in March 1963; this horizon was detected by dielectric profiling and electrical conductivity measurements: the proof by chemical analysis has still to be seen. At the ten investigated sites on Amundsenisen the 1964-65 horizon was identified 4.1-5.7 m below the surface. The accumulation rates on Amundsenisen are 41-91kg m-2 a−1 The cores are up to 100 years old A relationship between isotope content and the mean air temperature on a regional scale can be based on measurements of firn temperature at 10 m depth at the drilling sites Between Neumayer station at the coast and Heimefrontfiella, the temperature gradient of the deuterium content is 9.6%0 K−1. South of Heimefrontfiella, on the Amundsenisen plateau, it is only 5.5‰ K−1. Time series of yearly accumulation rates show no significant trend For the isotope records a significant trend to higher values with gradients of 0.1-0.2 δ2H‰a−1 can be seen in five of the ten time series

The paper presents first results from the upper 54m of a 723.91m ice core drilled on Akademii Nauk ice cap, Severnaya Zemlya, Eurasian Arctic, in 1999– 2001, supplemented by data from shallow ice cores. the glacier’s peculiarity is the infiltration and refreezing of meltwater, which changes the original isotopic and chemical signals. Therefore, stratigraphical observations in these ice cores are more difficult than in those from central Greenland or Antarctica. However, the 1963 maximum of artificial radioactivity from atmospheric nuclear tests is clearly detectable in the deep ice core, and the δ18O profile of a 12.82 m shallow core shows annual variations. Consequently, at least for the upper part of the main core, an almost seasonal time resolution of palaeoclimate record could be expected. the Chernobyl layer is detected by increased 137Cs activity at depths of 11.81–12.51m related to the AD 2000 surface. the resulting mean annual net mass balance is 53±2 g cm–2 a–1. Data from dielectric profiling of the main core show considerable peaks in conductivity; one of them is interpreted as a volcano event. According to the resulting chronology, this part of the core represents approximately the last 100 years.

The distribution of surface mass balance on Amundsenisen, Dronning Maud Land, Antarctica, is investigated along a continous profile line. Ice-penetrating radar is used to map variations in ice-layer thickness within the upper 100 m of the ice sheet. The route passes several firn- and ice-core drilling sites over a distance of 320 km. Dielectric-profiling data of ice cores are used to calculate the depths of selected reflection horizons and the cumulative mass of the ice column. The local surface mass balance is determined as a temporal average, covering a time-span of almost two centuries. The findings indicate a complex accumulation pattern superimposed on a generally low surface mass balance, which is related to small-scale surface undulations. The results of the radar soundings are in general in good agreement with surface mass-balance data derived from firn-core studies. Discrepancies between these two datasets can be explained by spatial mismatch or by minor quality of either ice-core profiles or radar data. For regional comparison of radar-based accumulation data we use an accumulation distribution interpolated from point measurements. The surface mass balance varies up to 50% over short distances, with correlation lengths of <10 km. We conclude that the current utilization schemes of point sampling are only capable of reproducing local values and regional trends but provide no information on the small-scale variability of surface mass balance.

Isochronic continuous horizons between 20 and 90 m depth in a ground-penetrating radar (GPR) profile, recorded in Dronning Maud Land, Antarctica, are identified by comparison of synthetic and measured single radar traces. The measured radar-gram is derived from a stacked GPR profile; the synthetic radargram is computed by convolution of the complex reflection coefficient profile, based on dielectric profiling (DEP) data of a 150 m ice core, with a depth-invariant wavelet. It reproduces prominent reflections of the measured radargram to a considerable degree. Analyzing matching peaks in both radargrams enables us to identify isochronic reflections and transfer individual volcanic-event datings to the GPR profile. Reflections are primarily caused by changes in permittivity; changes in conductivity are of minor importance. However, several peaks in permittivity andconductivity show a good correlation and indicate that some reflections are related to acidic layers. The results demonstrate the possibility of reproducing radargrams from ice-core property profiles, a necessary step for the interpretation of remotely sensed radar data and the general significance of connecting ice-core and radar data for correct interpretations. Problems related to forward modeling, data gaps, origin of permittivity peaks, and GPR profiles used for comparison, are discussed.

The European Project for Ice Coring in Antarctica (EPICA) includes a comprehensive pre-site survey on the inland ice plateau of Dronning Maud Land. This paper focuses on the investigation of the 18O content of shallow firn and ice cores. These cores were dated by profiles derived from dielectric-profiling and continuous flow analysis measurements. the individual records were stacked in order to obtain composite chronologies of 18O contents and accumulation rates with enhanced signal-to-noise variance ratios. These chronologies document variations in the last 200 and 1000 years. The18O contents and accumulation rates decreased in the 19th century and increased during the 20th century. Using the empirical relationships between stable isotopes, accumulation rates and the 10 m firn temperature, the variation of both parameters can be explained by the same temperature history. But other causes for these variations, such as the build-up of the snow cover, cannot be excluded. A marked feature of the 1000 year chronology occurs during the period AD 1180–1530 when the 18Ocontents remains below the long-term mean. Cross-correlation analyses between five cores from the Weddell Sea region and Dronning Maud Land show that 18O records can in some periods be positively correlated and in others negatively correlated, indicating a complex climatic history in time and space.

Clear evidence for the formation of mixed clathrate hydrates of air and hydrochlorofluorocarbon densifier (known as HCFC-141b, sometimes also called R-141b) is found by means of synchrotron X-ray diffraction and Raman spectroscopy on a sample recovered from the bottom of the EPICA Dronning Maud Land deep borehole in Antarctica. Subglacial water (SGW) appears to have reacted with the drilling liquid to build a large lump of clathrate hydrate. The hydrate growth may well have been accelerated by the stirring of the SGW–densifier mixture during drilling. Moreover, dissolved air in the SGW appears to have participated in the formation of mixed hydrates of air and HCFC-141b as evidenced by the concomitant appearance of Raman signals from both constituents. Our findings elucidate to some extent the meaning of earlier accounts of the formation of ‘heavy chips’ that may sink to the bottom of the borehole, possibly affecting or even impeding the drilling advance. These observations raise concerns with respect to the use of HCFC-141b densifiers in ice-core drilling liquids under warm ice conditions.

In the mid-1990s, excellent results from the GRIP and GISP2 deep drilling projects in Greenland opened up funding for continued ice-coring efforts in Antarctica (EPICA) and Greenland (NorthGRIP). The Glaciology Group of the Niels Bohr Institute, University of Copenhagen, was assigned the task of providing drilling capability for these projects, as it had done for the GRIP project. The group decided to further simplify existing deep drill designs for better reliability and ease of handling. The drill design decided upon was successfully tested on Hans Tausen Ice Cap, Peary Land, Greenland, in 1995. The 5.0m long Hans Tausen (HT) drill was a prototype for the ~11m long EPICA and NorthGRIP versions of the drill which were mechanically identical to the HT drill except for a much longer core barrel and chips chamber. These drills could deliver up to 4m long ice cores after some design improvements had been introduced. The Berkner Island (Antarctica) drill is also an extended HT drill capable of drilling 2 m long cores. The success of the mechanical design of the HT drill is manifested by over 12 km of good-quality ice cores drilled by the HT drill and its derivatives since 1995.

Based on ground-penetrating radar profiles, we analyze area-wide spatial and temporal characteristics of accumulation rate in the vicinity of the EPICA (European Project for Ice Coring in Antarctica) deep-drilling site in Dronning Maud Land, Antarctica (EDML). An area of 1600km2 is covered by 500km of radar profiles, organized in a star-like pattern with eight 20–25km legs and a 10km grid with 1–3km spacing, each pattern being centred on the EDML drilling location. Distributions of density, cumulative mass, age and the electromagnetic wave speed with depth are available from physical ice-core records. Nine internal reflection horizons are continuously tracked within the upper 110m of ice over the whole area, yielding a spatial picture of accumulation rate history over >1000 years. The mean accumulation rate over the last 153 years varies between 50 and 75 kgm–2 a–1 over 50 km perpendicular to the ice divide; the spatial average is ~61 kgm–2 a–1. This general pattern is overlain by small-scale variations of accumulation rate on the order of 10% of the mean. Maximum local gradients in accumulation rate are ~2–3 kgm–2 a–1 km–1, about five times the regional accumulation rate gradient. Comparison of topography and accumulation rate along a 20 km profile in the direction of the mean winds indicates that variations in accumulation rate over short distances are linked to surface undulations. Our results show that advected spatial variations of accumulation rate are on the same order and even exceed temporal changes over the investigated periods. Ice flow and upstream effects therefore might influence accumulation rates reconstructed from the EDML ice core.

Between 1999 and 2001, a 724 m long ice core was drilled on Akademii Nauk, the largest glacier on Severnaya Zemlya, Russian Arctic. The drilling site is located near the summit. The core is characterized by high melt-layer content. The melt layers are caused by melting and even by rain during the summer. We present high-resolution data of density, electrical conductivity (dielectrical profiling), stable water isotopes and melt-layer content for the upper 136m (120 m w.e.) of the ice core. The dating by isotopic cycles and electrical conductivity peak identification suggests that this core section covers approximately the past 275 years. Singularities of volcanogenic and anthropogenic origin provide well-defined additional time markers. Long-term temperatures inferred from 12 year running mean averages of δ18O reach their lowest level in the entire record around 1790. Thereafter the δ18O values indicate a continuously increasing mean temperature on the Akademii Nauk ice cap until 1935, interrupted only by minor cooling episodes. The 20th century is found to be the warmest period in this record.

This paper presents a new compilation of gridded datasets for three-dimensional modelling of the Antarctic ice sheet. These are for surface elevation, ice thickness, bedrock elevation and accumulation rate as interpolated on a 281 × 281 mesh with 20 km spacing, and encompass all the ice sheet and surrounding continental shelf. Data sources include the Bamber digital-elevation model from ERS-1 radar-altimeter data, a redigitization of available ice-thickness data, the Giovinetto accumulation data, recent ice-thickness data from British and German expeditions as well as accumulation data from German and Norwegian expeditions. In particular, new data were incorporated for the Filchner-Ronne Ice Shelf and for Dronning Maud Land, Antarctica, arising from the EPICA pre-site survey. Special attention was devoted to matching the various data sources carefully, both among themselves and across the grounding line and below the ice shelves, to enable ice-sheet expansion and retreat in dynamic situations. As an application, the balance flow is calculated over the entire ice sheet using a two-dimensional finite-difference scheme and compared with a previous assessment. This brought to light the existence of ice-streaming features extending well inland. A detailed zoom over Dronning Maud Land exhibits the general flow characteristics of interest for locating a future deep-drilling site. As a by-product, an updated value of 26.4 × 106km3 was obtained for the total volume of the ice sheet and ice shelves, or equivalent to 61.1 m of global sea-level rise after removal of the ice sheet and subsequent oceanic invasion and isostatic rebound. The total accumulation over the grounded ice sheet, including the Antarctic Peninsula, is 1924 Gta−1, or between 5 and 20% higher than earlier estimates. Including all the ice shelves, the value is 2344 Gt a−1.

The densification of dry polar snow and firn results in a continuous increase of density with depth accompanied by significant density fluctuations within seasonal layers. Density measurements of high spatial resolution reveal a persistent minimum of density fluctuations in the vicinity of the snow–firn transition (0.55–0.65 g cm-3) in firn-core records. In this study we give an explanation for the fluctuation minimum by applying a new method of X-ray microtomography to obtain three-dimensional (3-D) structural data of a Greenland firn core. At 13 different depths between 10 and 78 m a set of 16 samples of 40 cm total length for each depth interval was measured. A reconstructed firn segment of 40 cm covers 1–2 years of snow accumulation. Using digital image analysis techniques, different structural parameters are estimated including 3-D pore and particle sizes and specific surface areas. It is shown that the densification rates of snow and firn layers consisting of coarse particles are much higher than those consisting of fine particles within the same depth interval. This causes a density crossing of fine- and coarse-grained layers with a minimum of density variations at the crossover point. This crossing-over implies that formerly dense layers in the seasonal density signal are not of the same origin as dense layers in the deeper part of the firn column and that the seasonal density signal will totally change shape with depth. It is speculated that in coarse- and fine-grained firn the dominant mechanism of densification acts over different regimes of density.

A deep ice core has been drilled on Akademii Nauk ice cap, Severnaya Zemlya, Eurasian Arctic. High-resolution chemical analysis has been carried out for the upper 53 m of this ice core to study its potential as an atmospheric aerosol archive, despite strong meltwater percolation. These records show that a seasonal atmospheric signal cannot be deduced. However, strong year-to-year variations have allowed the core to be dated, and a mean annual net mass balance of 0.46 m w.e. a-1 was deduced. The chemical signature of an extraordinarily high peak in electrical conductivity at 26 m depth pointed clearly to the eruption of Bezymianny, Kamchatka, in 1956. However, in general, peaks in the electrical conductivity are not necessarily related to deposition of volcanogenic sulphur aerosol. In contrast, maximum sulphate and nitrate concentrations in the ice could be related to maximum SO2 and NOx anthropogenic emissions in the 1970s, probably caused by the nickel- and copper-producing industries in Norilsk and on the Kola peninsula or by industrial combustion processes occurring in the Siberian Arctic. In addition, during recent decades sulphate and nitrate concentrations declined by 80% and 60%, respectively, reflecting a decrease in anthropogenic pollution of the Arctic basin.